Capped dual-headed organoaluminum compositions

ABSTRACT

The present disclosure relates to a capped dual-headed organoaluminum composition having the formula (I) and processes to prepare the same. In at least one aspect, the capped dual-headed organoaluminum compositions can be used in olefin polymerization.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to, and the benefit of, U.S.provisional application No. 62/611,656, which was filed on Dec. 29,2017, and is incorporated herein in its entirety.

FIELD

Embodiments relate to capped dual-headed organoaluminum compositions andprocesses to prepare the same. Such compositions may be capable of chainshuttling and/or chain transfer. In at least one aspect, the cappeddual-headed organoaluminum compositions can be used in olefinpolymerization.

BACKGROUND

In recent years, advances in polymer design have been seen with the useof compositions capable of chain shuttling and/or chain transfer. Forexample, chain shuttling agents having reversible chain transfer abilitywith transition metal catalysts have enabled the production of novelolefin block copolymers (OBCs). Currently, the best known compositionscapable of chain shuttling and/or chain transfer are simple metal alkylsthat typically contain only a single point of attachment to the metalfor each polymer chain, such as diethyl zinc which produces polymerchains terminated with zinc metal at one end. More sophisticatedcompositions capable of chain shuttling and/or chain transfer, such asdual-headed chain shuttling agents, with the alkane moiety attached totwo metals, are also known. Indeed, dual-headed compositions capable ofchain shuttling and/or chain transfer are of great interest since theycan enable the production of new polyolefins, such as telechelicfunctional polymers, triblock copolymers, etc. However, significantchallenges exist for using such dual-headed compositions to producehighly pure telechelic polymer chains in reactors.

SUMMARY

In certain embodiments, this disclosure relates to a capped dual-headedorganoaluminum composition of formula (I):

wherein:

n is a number from 1 to 100;

Y is a linking group composed of a linear, branched, or cyclic C₄ toC₁₀₀ hydrocarbylene group that optionally includes at least oneheteroatom and that is aliphatic or aromatic, wherein Y comprises twopoints of attachment to Al atoms and at least one of the two points ofattachments is —CH₂—;

each R group is independently a substituted or unsubstituted aryl groupor a substituted or unsubstituted cyclic alkyl group containing,optionally, at least one heteroatom; and

two R groups attached to the same Al atom can be optionally covalentlylinked together.

In further embodiments, this disclosure relates to a process forpreparing a capped dual-headed organoaluminum composition of formula(I), the process comprising: (a) combining an aluminum compound, alinking agent, a capping agent, and an optional solvent, and (b)obtaining the capped dual-headed organoaluminum composition of formula(I), wherein:

the aluminum compound has the formula Al(J)₃, wherein each J group isindependently hydrogen, a substituted or unsubstituted alkyl group, or asubstituted or unsubstituted aryl or heteroaryl group, wherein at leastone J group is hydrogen or an acyclic alkyl group, and, optionally, twoJ groups can be covalently linked together;

the linking agent is a C₄ to C₁₀₀ hydrocarbon comprising either at leasttwo vinyl groups or a vinyl group and a cyclic olefin group and,optionally, includes at least one heteroatom; and

the capping agent is a substituted or unsubstituted cyclic olefin.

In further embodiments, this disclosure relates to a capped dual-headedorganoaluminum composition of formula (I) comprising the reactionproduct of an aluminum compound, a linking agent, a capping agent, andan optional solvent, wherein:

the aluminum compound has the formula Al(J)₃, wherein each J group isindependently hydrogen, a substituted or unsubstituted alkyl group, or asubstituted or unsubstituted aryl or heteroaryl group, wherein at leastone J group is a hydrogen or an acyclic alkyl group, and, optionally,two J groups can be covalently linked together;

the linking agent is a C₄ to C₁₀₀ hydrocarbon comprising either at leasttwo vinyl groups or a vinyl group and a cyclic olefin group and,optionally, includes at least one heteroatom; and

the capping agent is a substituted or unsubstituted cyclic olefin.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is the ¹H NMR spectra for Example 1.

FIG. 2 is the GC/MS spectrum for Example 1.

FIGS. 3A and 3B are the ¹H NMR spectra for Example 2.

FIG. 4 is the GC/MS spectrum for Example 2.

FIG. 5 is the GC/MS spectrum for Example 3.

FIGS. 6A, 6B, and 6C are the ¹H NMR spectra for Example 4.

FIG. 7 is the ¹³C NMR spectrum of polyethylene synthesized in thepresence of the capped dual-headed organoaluminum composition of Example3.

FIG. 8 is the GPC chromatogram of polyethylene synthesized in thepresence of the capped dual-headed organoaluminum composition of Example3.

DEFINITIONS

All references to the Periodic Table of the Elements refer to thePeriodic Table of the Elements published and copyrighted by CRC Press,Inc., 2003. Also, any references to a Group or Groups shall be to theGroup or Groups reflected in this Periodic Table of the Elements usingthe IUPAC system for numbering groups. Unless stated to the contrary,implicit from the context, or customary in the art, all parts andpercentages are based on weight and all test methods are current as ofthe filing date of this disclosure. For purposes of United States patentpractice, the contents of any referenced patent, patent application orpublication are incorporated by reference in their entirety (or itsequivalent U.S. version is so incorporated by reference in itsentirety), especially with respect to the disclosure of synthetictechniques, product and processing designs, polymers, catalysts,definitions (to the extent not inconsistent with any definitionsspecifically provided in this disclosure), and general knowledge in theart.

Number ranges in this disclosure are approximate and, thus, may includevalues outside of the ranges unless otherwise indicated. The numericalranges disclosed herein include all values from, and including, thelower and upper value. For ranges containing explicit values (e.g., 1,or 2, or 3 to 5, or 6, or 7), any subrange between any two explicitvalues is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).The numerical ranges disclosed herein further include the fractionsbetween any two explicit values

In the event the name of a compound herein does not conform to thestructural representation thereof, the structural representation shallcontrol.

The terms “chain shuttling agent” and “chain transfer agent” refer tothose known to one of ordinary skill in the art. Specifically, the term“shuttling agent” or “chain shuttling agent” refers to a compound ormixture of compounds that is capable of causing polymeryl transferbetween various active catalyst sites under conditions ofpolymerization. That is, transfer of a polymer fragment occurs both toand from an active catalyst site in a facile and reversible manner. Incontrast to a shuttling agent or chain shuttling agent, an agent thatacts merely as a “chain transfer agent,” such as some main-group alkylcompounds, may exchange, for example, an alkyl group on the chaintransfer agent with the growing polymer chain on the catalyst, whichgenerally results in termination of the polymer chain growth. In thisevent, the main-group center may act as a repository for a dead polymerchain, rather than engaging in reversible transfer with a catalyst sitein the manner in which a chain shuttling agent does. Desirably, theintermediate formed between the chain shuttling agent and the polymerylchain is not sufficiently stable relative to exchange between thisintermediate and any other growing polymeryl chain, such that chaintermination is relatively rare.

The term “derivative” used herein refers to the reaction product of achemical species after the insertion reaction of said chemical speciesinto metal alkyl or metal hydride bonds. For example, and withoutlimitation, the “Y” in (R)₂—Al[—Y^(C)—Al(R)]—R can define the derivativeof the linking agent CH₂═CH(CH₂)₆CH═CH₂ when said linking agent isreacted with Al(iBu)₃ to form (iBu)₂-Al[—CH₂(CH₂)₈CH₂—Al(iBu)]-iBu. Inthis non-limiting example, Y^(C) is —CH₂(CH₂)₈CH₂—, a linking groupwhich is the derivative of the linking agent CH₂═CH(CH₂)₆CH═CH₂ afterinsertion of said linking agent into Al—H bonds.

The term “linking agent” is a chemical species whose derivative linksmultiple metal species together in a molecule by inserting into a metalalkyl or metal hydride bond of each metal. In the above non-limitingexample, CH₂═CH(CH₂)₆CH═CH is a linking agent which joins n+1 aluminumspecies to form the species (iBu)₂-Al[—CH₂(CH₂)₈CH₂—Al(iBu)]-iBu. Afterinsertion, the linking agent becomes the linking group —CH₂(CH₂)₈CH₂—.

The terms “capped” or “capping group” refer to the derivative of a“capping agent,” where the capping agent forms a more stericallyhindered metal alkyl/aryl bond such that the rate of further chaintransfer or chain shuttling reactions from this derivative is very low.For example, and without limitation, the R groups of the composition offormula (I) are capping groups which are derivatives of capping agents,where the capping agents are substituted or unsubstituted cyclicolefins, optionally containing at least one heteroatom.

With reference to the composition of formula (I) or any structuralformulae falling within formula (I), the symbol * used herein refers toa carbon-metal bond serving as the point of attachment between thecarbon of a substituent group and the aluminum metal of the compositionof formula (I).

“Co-catalysts” refers to compounds that can activate a procatalyst toform an active catalyst composition/system capable of polymerization ofunsaturated monomers. “Co-catalyst” is used interchangeably with“activator” and like terms.

“Procatalyst” refers to a transition metal compound that, when combinedwith an activator, is capable of polymerization of unsaturated monomers.Suitable procatalysts for the present disclosure include those thateither require or do not require a co-catalyst to become an activecatalyst capable of polymerizing unsaturated monomers. “Procatalyst” isused interchangeably with “catalyst precursor,” “transition metalcatalyst,” “transition metal catalyst precursor,” “metal complex,” andlike terms. Suitable procatalysts include those known in the art, suchas those disclosed in WO 2005/090426, WO 2005/090427, WO 2007/035485, WO2009/012215, WO 2014/105411, U.S. Patent Publication Nos. 2006/0199930,2007/0167578, 2008/0311812, and U.S. Pat. Nos. 7,355,089 B2, 8,058,373B2, and 8,785,554 B2, all of which are incorporated herein by referencein their entirety.

“Catalyst system” refers to a procatalyst or the combination of aprocatalyst and an activator, with or without a support, capable ofolefin polymerization. “Catalyst system” is used interchangeably with“active catalyst,” “active catalyst composition,” “olefin polymerizationcatalyst,” and like terms.

“Polymer” refers to a compound prepared by polymerizing monomers,whether of the same or a different type. The generic term polymer thusembraces the term homopolymer, usually employed to refer to polymersprepared from only one type of monomer, and the term interpolymer asdefined below. It also embraces all forms of interpolymers, e.g.,random, block, homogeneous, heterogeneous, etc.

“Interpolymer” and “copolymer” refer to a polymer prepared by thepolymerization of at least two different types of monomers. Thesegeneric terms include both classical copolymers, i.e., polymers preparedfrom two different types of monomers, and polymers prepared from morethan two different types of monomers, e.g., terpolymers, tetrapolymers,etc.

The term “block copolymer” or “segmented copolymer” refers to a polymercomprising two or more chemically distinct regions or segments (referredto as “blocks”) joined in a linear manner, that is, a polymer comprisingchemically differentiated units which are joined (covalently bonded)end-to-end with respect to polymerized functionality, rather than inpendent or grafted fashion. The blocks differ in the amount or type ofcomonomer incorporated therein, the density, the amount ofcrystallinity, the type of crystallinity (e.g., polyethylene versuspolypropylene), the crystallite size attributable to a polymer of suchcomposition, the type or degree of tacticity (isotactic orsyndiotactic), regio-regularity or regio-irregularity, the amount ofbranching, including long chain branching or hyper-branching, thehomogeneity, and/or any other chemical or physical property. The blockcopolymers are characterized by unique distributions of both polymerpolydispersity (PDI or Mw/Mn) and block length distribution, e.g., basedon the effect of the use of a shuttling agent(s) in combination withcatalyst systems.

DETAILED DESCRIPTION

All schemes and discussions below are by way of example only and are notmeant to be limiting in any way. As noted herein, dual-headedcompositions are of great interest since they can enable production oftelechelic functional polymers. For example, and without limitation,reference is made to non-limiting Structure 1. Structure 1 represents anexemplary dual-headed composition with a Y linking group sandwichedbetween two aluminum atoms. Y may be, for example, a linear, branched,or cyclic C₄ to C₁₀₀ hydrocarbylene group that optionally includes atleast one heteroatom (B, O, S, N, F, Cl or Si) and that is aliphatic oraromatic. The Y linking group links two separate Al atoms and isattached to each Al atom via points of attachment. The points ofattachment are groups within (i.e., fragments of) the Y linking group,and at least one point of attachment is an ethylene group, —CH₂—. Eachof the terminal R groups may be a substituted or unsubstituted arylgroup or a substituted or unsubstituted cyclic alkyl group and may,optionally, include at least one heteroatom. Two R groups attached tothe same Al atom can be optionally covalently linked together. The Ylinking group can then, during olefin polymerization, grow into apolymer chain with both terminal ends of the chain bonded to thealuminum atoms via terminal polymeryl-metal bonds. Subsequently, theterminal polymeryl-metal bonds may be transformed to desired functionalgroups via functionalization chemistry, thereby resulting in a desireddi-functional (telechelic) polymer chain. The composition ofnon-limiting Structure 1 may be in monomeric (n=1) or oligomeric (n>1)forms.

Structure 1 contains capping groups (R) that have very low rates ofchain transfer or chain shuttling with a catalyst and will, therefore,not grow into polymer chains (i.e., no unwanted mono-functional chainsare produced). Specifically, as seen in the composition of formula (I),the terminal R groups (capping groups) may form sterically hinderedmetal-carbon bonds such that chain transfer or chain shuttling on thesesterically hindered sites are kinetically disfavored in competition withthe less hindered bonds between the metal atoms and the Y linking group(i.e., the derivative of a linking agent). Accordingly, unwantedmono-functional polymer chains are prevented from growing, as thecapping groups make the chain transfer or chain shuttling reaction andpolymer growth occur selectively on the less-hindered, Y linking groupof the composition of formula (I). As a result, only desireddi-functional polymer chains will grow from the Y linking group viaolefin polymerization and functionalization, thereby enabling puretelechelic polymers.

If the R groups of Structure 1 were simple alkyl groups rather thancapping groups, they could lead to monofunctional polymer chains bychain transfer polymerization. A way to reduce the amount of unwantedmono-functional polymer chains relative to the desired di-functionalpolymer chains (grown from the Y linking group) is to increase the (n)value of the composition; however, such an approach would result inhigher in-reactor molecular weight chains which would cause reactoroperability issues (e.g., high viscosity), especially for solutionprocesses. Accordingly, the use of capping groups (R) is important asthis allows for the formation of highly pure difunctional polymersexclusively from the Y linking group.

Process for Preparing Capped Dual-Headed Organoaluminum Compositions

The composition of formula (I) can be prepared from the reactionresulting from combining an aluminum compound, a linking agent, and acapping agent. In certain embodiments, the capping group can be part ofthe aluminum compound; thus the composition of formula (I) can beprepared from the reaction resulting from combining an aluminum compoundand a linking agent. In this case, the R groups of formula (I) will be Jgroups instead. These reactions can occur in the absence of (neat) or inthe presence of solvent(s). Suitable solvents include but are notlimited to non-polar solvents, such as xylenes, toluene, hexane,pentane, benzene, or combinations thereof.

Accordingly, the composition of formula (I) can be prepared by a processcomprising: (a) combining an aluminum compound, a linking agent, acapping agent, and an optional solvent (or, in certain embodiments,combining an aluminum compound, a linking agent, and an optionalsolvent), and (b) obtaining the composition of formula (I), wherein: thealuminum compound has the formula Al(J)₃, where each J group isindependently hydrogen, a substituted or unsubstituted alkyl group, or asubstituted or unsubstituted aryl or heteroaryl group, wherein at leastone J group is hydrogen or an acyclic alkyl group, and, optionally, twoJ groups can be covalently linked together; the linking agent is a C₄ toC₁₀₀ hydrocarbon comprising either at least two vinyl groups or a vinylgroup and a cyclic olefin group and, optionally, includes at least oneheteroatom; and the capping agent is a substituted or unsubstitutedcyclic olefin.

The reaction resulting from combining an aluminum compound, a linkingagent, a capping agent, and an optional solvent (or, in certainembodiments, combining an aluminum compound, a linking agent, and anoptional solvent) may be conducted at a temperature of from 50° C. to200° C., or from 80° C. to 180° C., or from 100° C. to 150° C. Theseelevated temperatures facilitate the removal of the J groups (e.g.,alkyl groups) of the aluminum compound via beta-hydride eliminationresulting in insertion of the linking agent and the capping agent intothe resulting Al—H bonds to form the composition of formula (I).

Accordingly, in certain embodiments, the composition of formula (I) canbe prepared by a process comprising: (a) combining an aluminum compound,a linking agent, a capping agent, and an optional solvent (or, incertain embodiments, combining an aluminum compound, a linking agent,and an optional solvent) at a temperature of from 50° C. to 200° C. (orfrom 80° C. to 180° C. or from 100° C. to 150° C.), and (b) obtainingthe composition of formula (I), wherein: the aluminum compound has theformula Al(J)₃, where each J group is independently hydrogen, asubstituted or unsubstituted alkyl group, or a substituted orunsubstituted aryl or heteroaryl group, wherein at least one J group ishydrogen or an acyclic alkyl group, and, optionally, two J groups can becovalently linked together; the linking agent is a C₄ to C₁₀₀hydrocarbon comprising either at least two vinyl groups or a vinyl groupand a cyclic olefin group and, optionally, includes at least oneheteroatom; and the capping agent is a substituted or unsubstitutedcyclic olefin.

The reaction resulting from combining an aluminum compound, a linkingagent, a capping agent, and an optional solvent (or, in certainembodiments, combining an aluminum compound, a linking agent, and anoptional solvent) may require a reaction period of from 30 minutes to200 hours depending on the temperature at which the reaction isconducted. For example, and without limitation, a reaction period of 1to 2 hours may be needed if the reaction is conducted at 150° C., areaction period of 2 to 5 hours may be needed if the reaction isconducted at 120° C., and a reaction period of 20 to 200 hours may beneeded if the reaction is conducted at 60° C.

Accordingly, in certain embodiments, the composition of formula (I) canbe prepared by a process comprising: (a) combining an aluminum compound,a linking agent, and an optional solvent (or, in certain embodiments,combining an aluminum compound, a linking agent, and an optionalsolvent) at a temperature of from 50° C. to 200° C. (or from 80° C. to180° C. or from 100° C. to 150° C.) for a period of from 30 minutes to200 hours (or from 30 minutes to 100 hours, or from 1 hour to 50 hours,or from 1 hour to 30 hours, or from 1 hour to 25 hours, or from 1 hourto 15 hours, or from 1 hour to 10 hours, or from 1 hour to 5 hours), and(b) obtaining the composition of formula (I), wherein: the aluminumcompound has the formula Al(J)₃, where each J group is independentlyhydrogen, a substituted or unsubstituted alkyl group, or a substitutedor unsubstituted aryl or heteroaryl group, wherein at least one J groupis hydrogen or an acyclic alkyl group, and, optionally, two J groups canbe covalently linked together; the linking agent is a C₄ to C₁₀₀hydrocarbon comprising either at least two vinyl groups or a vinyl groupand a cyclic olefin group and, optionally, includes at least oneheteroatom; and the capping agent is a substituted or unsubstitutedcyclic olefin.

In certain embodiments of the process for preparing the composition offormula (I), the linking agent:aluminum compound:capping agent ratio isn:(n+1):(n+3), where n can be a number from 1 to 10. In certainembodiments of the process for preparing the composition of formula (I),the linking agent:aluminum compound ratio is n:(n+1), where n can be anumber from 1 to 10.

In the process for preparing the composition of formula (I), thealuminum compound, the linking agent, the capping agent, and theoptional solvent may be combined in any order. In certain embodiments,the aluminum compound, the linking agent, the capping agent, and theoptional solvent may be combined in one step. In further embodiments,the aluminum compound, the linking agent, the capping agent, and theoptional solvent may be combined in more than one step. For example, thealuminum compound, the capping agent, and the optional solvent may becombined first followed by subsequent addition of the linking agent; or,the aluminum compound, the linking agent, and the optional solvent maybe combined first followed by subsequent addition of the capping agent;or in certain embodiments where the capping agent is part of thealuminum compound, the aluminum compound, the linking agent, and theoptional solvent may be combined at the same time.

Aluminum Compound

Aluminum compounds are defined herein as compounds with the formulaAl(J)₃, where each J group independently is hydrogen, a substituted orunsubstituted alkyl group, or a substituted or unsubstituted aryl orheteroaryl group, wherein at least one J group is hydrogen or an acyclicalkyl group, and, optionally, two J groups can be covalently linkedtogether. Optionally, one J group, or each of two or three J groups, canbe a hydrogen atom. In certain embodiments, one J group, or each of twoor three J groups, is an acyclic alkyl group containing 1 to 30 carbonatoms or 2 to 20 carbon atoms. In certain embodiments, one J group, oreach of two or three J groups, is not hydrogen. In further embodiments,one J group, or each of two or three J groups, is not methyl. In furtherembodiments, one J group, or each of two or three J groups, is a C₁ toC₃₀ acyclic alkyl group or a C₂ to C₂₀ acyclic alkyl group. In certainembodiments, one J group, or each of two or three J groups, is abranched C₃ to C₃ acyclic alkyl group.

Suitable J groups include but are not limited to methyl, ethyl, propyl,isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, docecyl, aryl, and all isomers thereof. Trialkylaluminumcompounds and dialkylaluminum-hydride compounds are suitable reagents.Useful trialkylaluminum compounds include but are not limited totrimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropylaluminum, tributyl aluminum, trihexyl aluminum, triisohexyl aluminum,trioctyl aluminum, triisooctyl aluminum, tripentyl aluminum, tridecylaluminum, tribranched alkyl aluminums, tricycloalkyl aluminums,triphenyl aluminum, tritolyl aluminum, and the like. Usefuldialkylaluminum compounds include but are not limited todimethylaluminum-hydride, diethylaluminum-hydride,diisobutylaluminum-hydride, dibutylaluminum-hydride,dipropylaluminum-hydride, dihexylaluminum-hydride,diisohexylaluminum-hydride, dioctylaluminum-hydride,diisooctylaluminum-hydride, dipentylaluminum-hydride,didecylaluminum-hydride, dicycloalkyl aluminums,diphenylaluminum-hydride, ditolylaluminum-hydride, and the like.

Capping Groups

The terminal R groups of the composition of formula (I) are cappinggroups, which are derivatives of capping agents. In certain embodiments,the capping agents of this disclosure are substituted or unsubstitutedcyclic olefins or substituted or unsubstituted aryl group which,optionally, may contain at least one heteroatom. The cyclic olefins maybe monocyclic or polycyclic. Suitable cyclic olefins include but are notlimited to 5-ethylidene-2-norbornene (ENB), cyclohexene, norbornene,vinyl norbornene, norbornadiene, dicyclopentadiene, cyclopentene,cycloheptene, cyclooctene, cyclooctadiene, cyclododecene,1,2-dihydronaphthalene, 1,4-dihydronaphthalene, benzonorbornadiene,7-oxanorbornene, 7-oxanorbornadiene, and substituted derivativesthereof.

In certain embodiments, the terminal R groups (i.e., capping groups) ofthe composition of formula (I) are derivatives of cyclic olefins, whichare alkenes that form sterically hindered metal-carbon bonds. In furtherembodiments, the terminal R groups (i.e., capping groups) of thecomposition of formula (I) are derivatives of cyclic olefins, whereinthe cyclic olefins (i.e., capping agents) are selected from the groupconsisting of the following structures CA1 to CA4:

wherein:

-   -   each X₂, X₃, X₄, and X₅ is independently hydrogen, a substituted        or unsubstituted C₁ to C₂₀ alkyl, alkylene or alkylidene group,        or a substituted or unsubstituted C₆ to C₂₀ aryl group;    -   each X₂, X₃, X₄, and X₅ optionally includes at least one        heteroatom; and

in each of structures CA1 to CA3, two of the groups selected from X₂,X₃, X₄, and X₅ may optionally join to form cyclic structures.

In certain embodiments, the terminal R groups (i.e., capping groups) ofthe composition of formula (I) are selected from derivatives of cyclicolefins, wherein the cyclic olefins (i.e., capping agents) are selectedfrom the group consisting of the following structures CA5 to CA10:

Accordingly, in certain embodiments, the composition of formula (I)comprises terminal R groups (i.e., capping groups) that are selectedfrom the group consisting of the following structures CG1 to CG4:

wherein:

-   -   R₁ is hydrogen or a C₁ to C₂ alkyl group;    -   each X₂, X₃, X₄, and X₅ is independently hydrogen, a substituted        or unsubstituted C₁ to C₂₀ alkyl, alkylene or alkylidene group,        or a substituted or unsubstituted C₆ to C₂₀ aryl group;    -   each X₂, X₃, X₄, and X₅ optionally includes at least one        heteroatom; and

in each of structures CG1 to CG3, two of the groups selected from X₂,X₃, X₄, and X₅ may optionally join to form cyclic structures.

With reference to the above definitions, the symbol * refers to acarbon-metal bond serving as the point of attachment between the carbonof a capping group and the aluminum metal of the composition of formula(I).

In further embodiments, the composition of formula (I) comprisesterminal R groups (i.e., capping groups) that are selected from thegroup consisting of the following structures CG5 to CG13:

wherein R₁ is hydrogen or a C₁ to C₂ alkyl group.

In certain embodiments, R₁ of the terminal R groups (i.e., cappinggroups) of the composition of formula (I) may be methyl, ethyl,n-propyl, n-butyl, isobutyl, n-hexyl, isohexyl, n-octyl, or isooctyl.

Linking Group

In the composition of formula (I), Y is a linking group, which is alinear, branched, or cyclic C₄ to C₁₀₀ hydrocarbylene group thatoptionally includes at least one heteroatom and that is aliphatic oraromatic. Linking group Y is the derivative of a linking agent, whereinthe linking agent is a C₄ to C₁₀₀ hydrocarbon comprising either at leasttwo vinyl groups or a vinyl group and a cyclic olefin group and,optionally, includes at least one heteroatom. Suitable linking agentsmust be able to insert into aluminum-hydride bonds such that derivativesof the linking agents are sandwiched between two aluminum atoms. Asdiscussed above, Y of the composition of formula (I) is a linking groupthat can transfer to an active catalyst and grow during olefinpolymerization into a polymer chain as a result of chain transfer/chainshuttling between the active catalyst and the aluminum species to form aprecursor for a telechelic polymer. Subsequent functionalization willthen result in formation of the telechelic polymer.

In certain embodiments, Y is the derivative of a diene. In other words,the linking agent is a diene. As used herein, the term diene refers toany compound that contains either two vinyl groups or a vinyl group anda cyclic olefin group and, optionally, includes at least one heteroatom.Examples of suitable dienes include hydrocarbon-based dienes,heteroatom-containing hydrocarbon-based dienes such as1,3-di(ω-alkenyl)-tetramethyldisiloxanes and di(ω-alkenyl)ethers anddienes containing aromatic fragments, such as divinylbenzene.

Suitable hydrocarbon-based dienes as referred to herein include but arenot limited to dienes having the formula CH₂═CH(CH₂)_(m)CH═CH₂ orCH₂═CH(Ar)_(m)CH═CH₂, including cyclic and bicyclic analogs thereof,where m is an integer from 0 to 20, and Ar is an aryl group. Examples ofthese hydrocarbon-based dienes include but are not limited to1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene,1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene,1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and the like,typically containing from 5 to 40 carbon atoms.

Heteroatom-containing hydrocarbon-based dienes as referred to hereininclude dienes which contain at least one B, O, S, N, F, Cl or Si atom,or a combination of atoms. Specific examples of heteroatom-containinghydrocarbon-based dienes include but are not limited to compounds havingthe formulas O[(CH₂)_(m)CH═CH₂]₂, S[(CH₂)_(m)CH═CH₂]₂,R^(A)N[(CH₂)_(m)CH═CH₂]₂, (R^(B))₂Si[(CH₂)_(m)CH═CH₂]₂,Ar[Si(R^(B))₂(CH₂)_(m)CH═CH₂]₂, (CH₂)_(m)[Si(R^(B))₂(CH₂)_(m)CH═CH₂]₂,(R^(B))₃SiOSiR^(B)[(CH₂)_(m)CH═CH₂]₂, and [Si(R^(B))₂(CH₂)_(m)CH═CH₂]₂O;wherein m in each occurrence is independently an integer from 0 to 20,inclusive, preferably 1 to 20 inclusive; R^(A) is H or a hydrocarbylhaving from 1 to 12 carbon atoms, inclusive; R^(B) in each occurrence isindependently a hydrocarbyl having from 1 to 12 carbon atoms, inclusive;and Ar is an aryl group.

Examples of heteroatom-containing hydrocarbon-based dienes include butare not limited to divinyldiphenylsilane,1,4-bis(dimethyl(vinyl)silyl)benzene,1,5-bis(dimethyl(vinyl)silyl)pentane, divinyl ether,di(2-propenyl)ether, di(3-butenyl)ether, di(4-pentenyl)ether,di(5-hexenyl)ether, divinyl amine, di(2-propenyl)amine,di(3-butenyl)amine, di(4-pentenyl) amine, di(5-hexenyl)amine, divinylmethylamine, di(2-propenyl)methylamine, di(3-butenyl)methylamine,di(4-pentenyl)methylamine, di(5-hexenyl)methylamine, divinyl thioether,di(2-propenyl)thioether), di(3-butenyl)thioether,di(4-pentenyl)thioether, di(5-hexenyl)thioether, divinyl dimethylsilane,di(2-propenyl) dimethylsilane, di(3-butenyl) dimethylsilane,di(4-pentenyl) dimethylsilane, di(5-hexenyl) dimethylsilane, and thelike, typically containing from 4 to 40 carbon atoms.

Further examples of suitable heteroatom containing hydrocarbon-baseddienes include but are not limited to the disiloxane compounds, such asthe 1,1- and the 1,3-isomers of divinyl tetramethyldisiloxane (alsoreferred to here as di(ethan-1,2-diyl) tetramethyldisiloxane),di(2-propenyl)tetramethyldisiloxane, di(3-butenyl)tetramethyldisiloxane,di(4-pentenyl)tetramethyldisiloxane, di(5-hexenyl)tetramethyldisiloxane,di(6-heptenyl)tetramethyldisiloxane, di(7-octenyl)tetramethyldisiloxane,di(8-nonenyl)tetramethyldisiloxane, di(9-decenyl)-tetramethyldisiloxane,divinyltetraethyldisiloxane, di(2-propenyl)tetraethyldisiloxane,di(3-butenyl)tetraethyldisiloxane, di(4-pentenyl)tetraethyldisiloxane,di(5-hexenyl)-tetraethyldisiloxane, di(6-heptenyl)tetraethyldisiloxane,di(7-octenyl)tetraethyldisiloxane, di(8-nonenyl)tetraethyldisiloxane,di(9-decenyl)tetraethyldisiloxane, and the like;

diene compounds containing one cyclic olefin or cyclic alkane such asvinyl norbornene, 1,3-divinylcyclopentane, and vinylcyclohexene;

halogen-containing diene compounds such as 3-chloro-1,4-pentadiene,3-bromo-3-methyl-1,4-pentadiene, 3-chloro-1,4-hexadiene,3-chloro-3-methyl-1,4-hexadiene, 3-bromo-4-methyl-1,4-hexadiene,3-chloro-5-methyl-1,4-hexadiene, 3-bromo-4,5-dimethyl-1,4-hexadiene,3-bromo-1,5-hexadiene, 3-chloro-3-methyl-1,5-hexadiene,3-bromo-1,5-heptadiene, 3-chloro-3-methyl-1,5-heptadiene,4-bromo-1,6-heptadiene, 3-chloro-4-methyl-1,6-heptadiene,4-bromo-1,6-octadiene, 3-chloro-4-methyl-1,6-octadiene,4-bromo-7-methyl-1,6-octadiene, 4-chloro-1,7-octadiene,3-chloro-4-methyl-1,7-octadiene, 4-bromo-1,7-nonadiene,4-bromo-4-methyl-1,7-nonadiene, 4-bromo-1,8-nonadiene, 3-chloro-4-methyl1,8-nonadiene, 5-bromo-1,8-decadiene, 3-chloro-5-methyl-1,8-decadiene,5-bromo-1,9-decadiene, 3-chloro-5-methyl-1,9-decadiene,5-bromo-1,10-undecadiene, and 5-bromo-1,1′-dodecadiene;

silane-containing dienes such as bis(vinyloxy)silane, dimethylbis(vinyloxy)silane, bisallyloxy silane, dimethylbis(allyloxy)silane,di(3-butenyl)dimethyl silane, bis(3-butenyloxy)silane,dimethylbis(3-butenyloxy)silane, di(4-pentenyl)dimethyl silane,bis(4-pentenyloxy)silane, bis(4-pentenyloxy)dimethylsilane,di(5-hexenyl)dimethylsilane, bis(5-hexenyloxy)silane, andbis(5-hexenyloxy)dimethylsilane;

ester-containing diene compounds such as 3-butenyl-4-pentenoate,4-pentenyl-4-pentenoate, 4-methoxycarbonyl-1,7-octadiene, and4-methoxycarbonyl-1,9-decadiene;

ether-containing diene compounds such as divinyl ether, diallyl ether,di(4-butenyloxy)ether, and di(5-hexenyloxy)ether; and

siloxy-containing diene compounds such as 4-trimethylsiloxymethyl-1,7-octadiene, and 4-trimethyl siloxymethyl-1,9-decadiene.

In further embodiments, Y is the derivative of conjugated dienecompounds such as 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene,1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,3-butadiene,1-phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene,2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1,3-butadiene,2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene,and 2-phenyl-1,3-butadiene.

In further embodiments, Y is the derivative of a triene or a C₄ to C₁₀₀hydrocarbon comprising three or more vinyl groups and optionallyincludes at least one heteroatom. In other words, the linking agent is atriene or a C₄ to C₁₀₀ hydrocarbon comprising three or more vinyl groupsand optionally includes at least one heteroatom. Suitable examplesinclude but are not limited to 1,4,7-octatriene,3-methyl-1,4,7-octatriene, 1,5,9-decatriene, 4-methyl-1,5,9-decatriene,1,2,4-trivinylcyclohexane, and the like. In certain embodiments, thelinking agent is 1,2,4-trivinylcyclohexane resulting in a composition offormula (I) having the following structural formulae with R as definedherein:

All linking groups discussed herein are generally available or can beproduced by known methods.

Polymerization Process

In certain embodiments, the composition of formula (I) can function as achain shuttling agent or a chain transfer agent during an olefinpolymerization process.

Accordingly, the present disclosure relates to a polymerization processfor the polymerization of at least one addition polymerizable monomer(i.e., olefin monomer) to form a polymer composition, the processcomprising: contacting at least one addition polymerizable monomer(olefin monomer) with a catalyst composition under polymerizationconditions; wherein the catalyst composition comprises the contactproduct (reaction product) of at least one catalyst precursor, anoptional co-catalyst, and the composition of formula (I).

The capped dual-headed organoaluminum compositions of formula (I) andcatalyst systems using the compositions of formula (I) described hereinare suitable for use in any prepolymerization and/or polymerizationprocess over a wide range of temperatures and pressures. Suchtemperatures and pressures, as well as other polymerization processinformation, described herein can be referred to as “polymerizationconditions.” The temperatures may be in the range of from 50° C. toabout 280° C., preferably from 50° C. to about 200° C. In anotherembodiment, the polymerization temperature is above 0° C., above 50° C.,above 80° C., above 100° C., above 150° C. or above 200° C. In anembodiment, the pressures employed may be in the range from 1 atmosphereto about 500 atmospheres or higher. Polymerization processes includesolution, gas phase, slurry phase and a high pressure process or acombination thereof.

In one embodiment, the present disclosure is directed toward a solution,high pressure, slurry or gas phase polymerization process of one or moreolefin monomers having from 2 to 30 carbon atoms, preferably 2 to 12carbon atoms, and more preferably 2 to 8 carbon atoms. The presentdisclosure is particularly directed to the polymerization of two or moreolefin monomers of ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene. Useful monomersinclude ethylenically unsaturated monomers, diolefins having 4 to 18carbon atoms, conjugated or nonconjugated dienes, polyenes, vinylmonomers and cyclic olefins. Non-limiting monomers may includenorbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane,styrenes, alkyl substituted styrene, ethylidene norbornene,dicyclopentadiene and cyclopentene. In another embodiment of thepolymerization process of the present disclosure, a copolymer ofethylene is produced, where with ethylene, a comonomer having at leastone alpha-olefin having from 4 to 15 carbon atoms, preferably from 4 to12 carbon atoms, and most preferably from 4 to 8 carbon atoms, ispolymerized in a solution process. In another embodiment of the processof the present disclosure, ethylene or propylene is polymerized with atleast two different comonomers, optionally one of which may be a diene,to form a terpolymer.

In one aspect of this disclosure, there is provided a polymerizationprocess and the resulting polymer, the process comprising polymerizingone or more olefin monomers in the presence of an olefin polymerizationcatalyst and the composition of formula (I) in a polymerization reactoror zone thereby causing the formation of at least some quantity of apolymer joined with the remnant of the composition of formula (I).Exemplary, non-limiting polymerization processes include those known inthe art, those disclosed in U.S. Pat. No. 8,501,885 B2, as well as thoseknown in the art for producing random copolymers. Exemplary,non-limiting polymerization processes include those conducted in asingle reactor or two reactors (parallel or series).

In yet another aspect, there is provided a process and the resultingpolymer, the process comprising polymerizing one or more olefin monomersin the presence of an olefin polymerization catalyst and the compositionof formula (I) in a polymerization reactor or zone thereby causing theformation of at least some quantity of an initial polymer joined withthe remnant of the composition of formula (I) within the reactor orzone; discharging the reaction product from the first reactor or zone toa second polymerization reactor or zone operating under polymerizationconditions that are distinguishable from those of the firstpolymerization reactor or zone; transferring at least some of theinitial polymer joined with the remnant of the composition of formula(I) to an active catalyst site in the second polymerization reactor orzone by means of at least one remaining shuttling site of thecomposition of formula (I); and conducting polymerization in the secondpolymerization reactor or zone so as to form a second polymer segmentbonded to some or all of the initial polymer by means of a remnant ofthe composition of formula (I), the second polymer segment havingdistinguishable polymer properties from the initial polymer segment.

During the polymerization, the reaction mixture is contacted with theactivated catalyst composition according to any suitable polymerizationconditions. The process can be generally characterized by use ofelevated temperatures and pressures. Hydrogen may be employed as a chaintransfer agent for molecular weight control according to knowntechniques, if desired. As in other similar polymerizations, it isgenerally desirable that the monomers and solvents employed be ofsufficiently high purity that catalyst deactivation or premature chaintermination does not occur. Any suitable technique for monomerpurification such as devolatilization at reduced pressure, contactingwith molecular sieves or high surface area alumina, or a combination ofthe foregoing processes may be employed.

Supports may be employed in the present methods, especially in slurry orgas-phase polymerizations. Suitable supports include solid,particulated, high surface area, metal oxides, metalloid oxides, ormixtures thereof (interchangeably referred to herein as an inorganicoxide). Examples include, but are not limited to talc, silica, alumina,magnesia, titania, zirconia, Sn₂O₃, aluminosilicates, borosilicates,clays, and any combination or mixture thereof. Suitable supportspreferably have a surface area as determined by nitrogen porosimetryusing the B.E.T. method from 10 to 1000 m²/g, and preferably from 100 to600 m²/g. The average particle size typically is from 0.1 to 500 μm,preferably from 1 to 200 μm, more preferably 10 to 100 μm.

In one aspect of the present disclosure, the catalyst and optionalsupport may be spray dried or otherwise recovered in solid, particulatedform to provide a composition that is readily transported and handled.Suitable methods for spray drying a liquid containing slurry are wellknown in the art and usefully employed herein. Preferred techniques forspray drying catalyst compositions for use herein are described in U.S.Pat. Nos. 5,648,310 and 5,672,669.

The polymerization is desirably carried out as a continuouspolymerization, for example, a continuous, solution polymerization, inwhich catalyst components, monomers, and optionally solvent, adjuvants,scavengers, and polymerization aids are continuously supplied to one ormore reactors or zones and polymer product continuously removedtherefrom. Within the scope of the terms “continuous” and “continuously”as used in this context include those processes in which there areintermittent additions of reactants and removal of products at smallregular or irregular intervals, so that, over time, the overall processis substantially continuous. The composition of formula (I) (if used)may be added at any point during the polymerization including in thefirst reactor or zone, at the exit or slightly before the exit of thefirst reactor, between the first reactor or zone and any subsequentreactor or zone, or even solely to the second reactor or zone. If thereexists any difference in monomers, temperatures, pressures or otherpolymerization conditions within a reactor or between two or morereactors or zones connected in series, polymer segments of differingcomposition such as comonomer content, crystallinity, density,tacticity, regio-regularity, or other chemical or physical differences,within the same molecule can be formed in the polymers of thisdisclosure. In such event, the size of each segment or block isdetermined by the polymer reaction conditions and typically is a mostprobable distribution of polymer sizes.

If multiple reactors are employed, each can be independently operatedunder high pressure, solution, slurry, or gas phase polymerizationconditions. In a multiple zone polymerization, all zones operate underthe same type of polymerization, such as solution, slurry, or gas phase,but, optionally, at different process conditions. For a solutionpolymerization process, it is desirable to employ homogeneousdispersions of the catalyst components in a liquid diluent in which thepolymer is soluble under the polymerization conditions employed. Onesuch process utilizing an extremely fine silica or similar dispersingagent to produce such a homogeneous catalyst dispersion wherein normallyeither the metal complex or the co-catalyst is only poorly soluble isdisclosed in U.S. Pat. No. 5,783,512. A high pressure process is usuallycarried out at temperatures from 100° C. to 4000° C. and at pressuresabove 500 bar (50 MPa). A slurry process typically uses an inerthydrocarbon diluent and temperatures of from 0° C. up to a temperaturejust below the temperature at which the resulting polymer becomessubstantially soluble in the inert polymerization medium. For example,typical temperatures in a slurry polymerization are from 30° C.,generally from 60° C. up to 115° C., including up to 100° C., dependingon the polymer being prepared. Pressures typically range fromatmospheric (100 kPa) to 500 psi (3.4 MPa).

In all of the foregoing processes, continuous or substantiallycontinuous polymerization conditions generally are employed. The use ofsuch polymerization conditions, especially continuous, solutionpolymerization processes, allows the use of elevated reactortemperatures which results in the economical production of the presentblock copolymers in high yields and efficiencies.

The catalyst may be prepared as a homogeneous composition by addition ofthe requisite metal complex or multiple complexes to a solvent in whichthe polymerization will be conducted or in a diluent compatible with theultimate reaction mixture. The desired co-catalyst or activator and,optionally, a composition of formula (I) may be combined with thecatalyst composition either prior to, simultaneously with, or aftercombination of the catalyst with the monomers to be polymerized and anyadditional reaction diluent. Desirably, if present, the composition offormula (I) is added at the same time.

At all times, the individual ingredients as well as any active catalystcomposition are protected from oxygen, moisture, and other catalystpoisons. Therefore, the catalyst components, the composition of formula(I), and activated catalysts are prepared and stored in an oxygen andmoisture free atmosphere, generally under a dry, inert gas such asnitrogen.

Without limiting in any way the scope of the disclosure, one means forcarrying out such a polymerization process is as follows. In one or morewell stirred tank or loop reactors operating under solutionpolymerization conditions, the monomers to be polymerized are introducedcontinuously together with any solvent or diluent at one part of thereactor. The reactor contains a relatively homogeneous liquid phasecomposed substantially of monomers together with any solvent or diluentand dissolved polymer. Preferred solvents include C₄₋₁₀ hydrocarbons ormixtures thereof, especially alkanes such as hexane or mixtures ofalkanes, as well as one or more of the monomers employed in thepolymerization. Examples of suitable loop reactors and a variety ofsuitable operating conditions for use therewith, including the use ofmultiple loop reactors, operating in series, are found in U.S. Pat. Nos.5,977,251, 6,319,989 and 6,683,149.

Catalyst along with co-catalyst and the composition of formula (I) arecontinuously or intermittently introduced in the reactor liquid phase orany recycled portion thereof at a minimum of one location. The reactortemperature and pressure may be controlled, for example, by adjustingthe solvent/monomer ratio or the catalyst addition rate, as well as byuse of cooling or heating coils, jackets or both. The polymerizationrate can be controlled by the rate of catalyst addition. The content ofa given monomer in the polymer product is influenced by the ratio ofmonomers in the reactor, which is controlled by manipulating therespective feed rates of these components to the reactor. The polymerproduct molecular weight is controlled, optionally, by controlling otherpolymerization variables such as the temperature, monomer concentration,or by the previously mentioned composition of formula (I), or a chainterminating agent such as hydrogen, as is known in the art.

In one aspect of the disclosure, a second reactor is connected to thedischarge of a first reactor, optionally by means of a conduit or othertransfer means, such that the reaction mixture prepared in the firstreactor is discharged to the second reactor without substantialtermination of polymer growth. Between the first and second reactors, adifferential in at least one process condition may be established.Generally, for use in formation of a copolymer of two or more monomers,the difference is the presence or absence of one or more comonomers or adifference in comonomer concentration. Additional reactors, eacharranged in a manner similar to the second reactor in the series may beprovided as well. Further polymerization is ended by contacting thereactor effluent with a catalyst kill agent such as water, steam or analcohol or with a coupling agent if a coupled reaction product isdesired.

The resulting polymer product is recovered by flashing off volatilecomponents of the reaction mixture such as residual monomer(s) ordiluent at reduced pressure, and, if necessary, conducting furtherdevolatilization in equipment such as a devolatilizing extruder. In acontinuous process the mean residence time of the catalyst and polymerin the reactor generally is from 5 minutes to 8 hours, for example, from10 minutes to 6 hours.

In a further aspect of this disclosure, alternatively, the foregoingpolymerization may be carried out in a plug flow reactor optionally witha monomer, catalyst, the composition of formula (I), temperature orother gradient established between differing zones or regions thereof,further optionally accompanied by separate addition of catalysts and/orthe composition of formula (I), and operating under adiabatic ornon-adiabatic polymerization conditions.

The use of functionalized derivatives of polymers are also includedwithin the present disclosure. Examples include polymers with Al terminiresulting from the composition of formula (I). Because a substantialfraction of the polymeric product exiting the reactor is terminated withmetal, further functionalization is relatively easy. The metallatedpolymer species can be utilized in well-known chemical reactions such asthose suitable for other alkyl-aluminum compounds to form amine-,hydroxy-, epoxy-, silane, vinylic, and other functionalized terminatedpolymer products. Polymers with Al termini can also be functionalizedvia thermal elimination of a di-unsaturated polymer by heating theAl-terminated polymer to temperatures causing beta-hydride elimination,preferably to 150-250° C. in the presence of sacrificial monomer, suchas ethylene, which reacts with the resulting aluminum-hydride species,preventing the eliminated di-unsaturated polymer from undergoing thereverse reaction (i.e. insertion into the aluminum-hydride species).

Olefin Monomers

Suitable monomers for use in preparing the polymer products of thepresent disclosure in polymerization processes include any additionpolymerizable monomer, generally any olefin or diolefin monomer.Suitable monomers can be linear, branched, acyclic, cyclic, substituted,or unsubstituted. In one aspect, the olefin can be any α-olefin,including, for example, ethylene and at least one differentcopolymerizable comonomer, propylene and at least one differentcopolymerizable comonomer having from 4 to 20 carbons, or4-methyl-1-pentene and at least one different copolymerizable comonomerhaving from 4 to 20 carbons. Examples of suitable monomers include, butare not limited to, straight-chain or branched α-olefins having from 2to 30 carbon atoms, from 2 to 20 carbon atoms, or from 2 to 12 carbonatoms. Specific examples of suitable monomers include, but are notlimited to, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene,1-hexane, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.Suitable monomers for use in preparing the copolymers disclosed hereinalso include cycloolefins having from 3 to 30, from 3 to 20 carbonatoms, or from 3 to 12 carbon atoms. Examples of cycloolefins that canbe used include, but are not limited to, cyclopentene, cycloheptene,norbornene, 5-methyl-2-norbornene, tetracyclododecene, and2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.Suitable monomers for preparing the copolymers disclosed herein alsoinclude di- and poly-olefins having from 3 to 30, from 3 to 20 carbonatoms, or from 3 to 12 carbon atoms. Examples of di- and poly-olefinsthat can be used include, but are not limited to, butadiene, isoprene,4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene,1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene,1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene,vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene.In a further aspect, aromatic vinyl compounds also constitute suitablemonomers for preparing the copolymers disclosed here, examples of whichinclude, but are not limited to, mono- or poly-alkylstyrenes (includingstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene),and functional group-containing derivatives, such as methoxystyrene,ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene,divinylbenzene, 3-phenylpropene, 4-phenylpropene and α-methylstyrene,vinylchloride, 1,2-difluoroethylene, 1,2-dichloroethylene,tetrafluoroethylene, and 3,3,3-trifluoro-1-propene, provided the monomeris polymerizable under the conditions employed.

Further, in one aspect, suitable monomers or mixtures of monomers foruse in combination with the composition of formula (I) disclosed hereinclude ethylene; propylene; mixtures of ethylene with one or moremonomers selected from propylene, 1-butene, 1-hexene,4-methyl-1-pentene, 1-octene, and styrene; and mixtures of ethylene,propylene and a conjugated or non-conjugated diene. In this aspect, thecopolymer or interpolymer can contain two or more intramolecular regionscomprising differing chemical or physical properties, especially regionsof differentiated comonomer incorporation, joined in a dimeric, linear,branched or polybranched polymer structure. Such polymers may beprepared by altering the polymerization conditions during apolymerization that includes a composition of formula (I), for exampleby using two reactors with differing comonomer ratios, multiplecatalysts with differing comonomer incorporation abilities, or acombination of such process conditions, and optionally a polyfunctionalcoupling agent.

Polymer Products

As disclosed herein, the polymer products refer to polymer products,after polymerization that are typically subjected to chemical treatmentto consume reactive metal alkyl groups and liberate the polymer productsfrom attachment to transition group or main group metals. This processcomprises hydrolysis with water to generate saturated polymer endgroups. Alternatively, addition of various organic or inorganic reagentsmay be added to both consume the metal alkyl groups and generatereactive functional end groups on the polymer chains.

The polymers produced by the processes of the present disclosure can beused in a wide variety of products and end-use applications. Thepolymers produced can be homo- and co-polymers of ethylene and propyleneand include linear low density polyethylene, elastomers, plastomers,high-density polyethylenes, medium density polyethylenes, low densitypolyethylenes, polypropylene, and polypropylene copolymers. Propylenebased polymers produced include isotactic polypropylene, atacticpolypropylene, and random, block or impact copolymers.

Utilizing the polymerization processes disclosed here, novel polymercompositions, including block copolymers of one or more olefin monomershaving the present molecular weight distribution, are readily prepared.Exemplary polymers comprise in polymerized form at least one monomerselected from ethylene, propylene, and 4-methyl-1-pentene.Illustratively, the polymers are interpolymers comprising in polymerizedform ethylene, propylene, or 4-methyl-1-pentene and at least onedifferent C2-20 α-olefin comonomer, and optionally one or moreadditional copolymerizable comonomers. Suitable comonomers are selectedfrom diolefins, cyclic olefins, and cyclic diolefins, halogenated vinylcompounds, vinylidene aromatic compounds, and combinations thereof.Exemplary polymers are interpolymers of ethylene with propylene,1-butene, 1-hexene or 1-octene. Illustratively, the polymer compositionsdisclosed here have an ethylene content from 1 to 99 percent, a dienecontent from 0 to 10 percent, and a styrene and/or C3-8 α-olefin contentfrom 99 to 1 percent, based on the total weight of the polymer. Thepolymers of the present disclosure may have a weight average molecularweight (Mw) from 500 to 2,500,000 in accordance with conventional GPCmethods. Typically, the polymers of the present disclosure have a weightaverage molecular weight (Mw) from 500 to 250,000 (e.g., from 2,000 to150,000, from 3,000 to 100,000, from 1,000 to 25,000, from 5,000 to25,000, etc.) in accordance with conventional GPC methods.

The polymers prepared according to this disclosure can have a meltindex, 12, from 0.01 to 2000 g/10 minutes, typically from 0.01 to 1000g/10 minutes, more typically from 0.01 to 500 g/10 minutes, andespecially from 0.01 to 100 g/10 minutes in accordance with ASTM D-792,Method B. Desirably, the disclosed polymers can have molecular weights,Mw, from 1,000 g/mol to 5,000,000 g/mol, typically from 1000 g/mol to1,000,000 g/mol, more typically from 1000 g/mol to 500,000 g/mol, andespecially from 1,000 g/mol to 300,000 g/mol in accordance withconventional GPC methods.

The density of the polymers of this disclosure can be from 0.80 to 0.99g/cc and typically, for ethylene containing polymers, from 0.85 g/cc to0.97 g/cc (e.g., from 0.853 to 0.970 g/cc), in accordance with ASTMD-792, Method B.

The polymers according to this disclosure may be differentiated fromconventional, random copolymers, physical blends of polymers, and blockcopolymers prepared via sequential monomer addition, fluxionalcatalysts, or by anionic or cationic living polymerization techniques,by, among other things, their narrow molecular weight distributions. Inthis aspect, for example, the polymer composition prepared according tothis disclosure can be characterized by a polydispersity index (PDI) offrom 1.5 to 10.0 (e.g, from 2.0 to 8.0, from 2.0 to 6.0, from 2.0 to5.0, from 2.0 to 4.0, etc.). For example, the polydispersity index (PDI)of the polymer composition can be from 1.5 to 2.8, from 1.5 to 2.5, orfrom 1.5 to 2.3.

If present, the separate regions or blocks within each polymer arerelatively uniform, depending on the uniformity of reactor conditions,and chemically distinct from each other. That is, the comonomerdistribution, tacticity, or other property of segments within thepolymer are relatively uniform within the same block or segment.However, the average block length can be a narrow distribution, but isnot necessarily so. The average block length can also be a most probabledistribution.

Illustratively, these interpolymers can be characterized by terminalblocks or segments of polymer having higher tacticity or crystallinityfrom at least some remaining blocks or segments. Illustratively, thepolymer can be a triblock copolymer containing a central polymer blockor segment that is relatively amorphous or even elastomeric.

In a still further aspect of this disclosure, there is provided apolymer composition comprising: (1) an organic or inorganic polymer,preferably a homopolymer of ethylene or of propylene and/or a copolymerof ethylene or propylene with one or more copolymerizable comonomers,and (2) a polymer or combination of polymers according to the presentdisclosure or prepared according to the process disclosed here.

The polymer products include combinations of two or more polymerscomprising regions or segments (blocks) of differing chemicalcomposition. In addition, at least one of the constituents of thepolymer combination can contain a linking group which is the remnant ofthe composition of formula (I), causing the polymer to possess certainphysical properties.

Various additives may be usefully incorporated into the presentcompositions in amounts that do not detract from the properties of theresultant composition. These additives include, for example, reinforcingagents, fillers including conductive and non-conductive materials,ignition resistant additives, antioxidants, heat and light stabilizers,colorants, extenders, crosslinkers, blowing agents, plasticizers, flameretardants, anti-drip agents, lubricants, slip additives, anti-blockingaids, anti-degradants, softeners, waxes, pigments, and the like,including combinations thereof.

The resultant polymers may be block interpolymers that can becharacterized by an average block index, e.g., as discussed in U.S. Pat.Nos. 7,947,793, 7,897,698, and 8,293,859. The resultant polymers may beblock composites that can be characterized by a block composite index,e.g., as discussed in U.S. Pat. Nos. 8,563,658, 8,476,366, 8,686,087,and 8,716,400. The resultant polymers may be crystalline blockcomposites that can be characterized by a crystalline block compositeindex, e.g., as discussed in U.S. Pat. Nos. 8,785,554, 8,822,598, and8,822,599. The resultant polymers may be specified block composites thatcan be characterized by a microstructure index, e.g., as discussed in WO2016/028957. The resultant polymers may be specified block compositesthat can be characterized by a modified block composite index, e.g., asdiscussed in WO 2016/028970.

In certain embodiments, the process for preparing the composition offormula (I) may be combined with functionalization chemistry to developtelechelic polymers. In certain embodiments, the composition of formula(I) can generate and grow telechelic polymer chains with both endsbonded to the composition of formula (I); subsequent transformation ofthe terminal polymeryl-metal bonds to desired di-end-functional groupsmay then occur to form the telechelic polymer.

Applications of the combination of the process for preparing thecomposition of formula (I) of the present disclosure withfunctionalization chemistry are in no way limited to development oftelechelic polymers and the above example. In certain embodiments, theprocess for preparing the composition of formula (I) of the presentdisclosure may be combined with, e.g., coordinative chain transferpolymerization, to produce functionalized polyolefins.

The polymers of the present disclosure may be blended and/or coextrudedwith any other polymer. Non-limiting examples of other polymers includelinear low density polyethylenes, elastomers, plastomers, high pressurelow density polyethylene, high density polyethylenes, isotacticpolypropylene, ethylene propylene copolymers and the like.

Polymers produced by the process of the present disclosure and blendsthereof are useful in such forming operations as film, sheet, and fiberextrusion and co-extrusion as well as blow molding, injection molding,roto-molding. Films include blown or cast films formed by coextrusion orby lamination useful as shrink film, cling film, stretch film, sealingfilm or oriented films.

EXAMPLES Methods

¹H NMR:

¹H NMR spectra are recorded on a Bruker AV-400 spectrometer at ambienttemperature. ¹H NMR chemical shifts in benzene-d₆ are referenced to 7.16ppm (C₆D₅H) relative to TMS (0.00 ppm).

¹³C NMR:

¹³C NMR spectra of polymers are collected using a Bruker 400 MHzspectrometer equipped with a Bruker Dual DUL high-temperature CryoProbe.The polymer samples are prepared by adding approximately 2.6 g of a50/50 mixture of tetrachloroethane-d₂/orthodichlorobenzene containing0.025M chromium trisacetylacetonate (relaxation agent) to 0.2 g ofpolymer in a 10 mm NMR tube. The samples are dissolved and homogenizedby heating the tube and its contents to 150° C. The data is acquiredusing 320 scans per data file, with a 7.3 second pulse repetition delaywith a sample temperature of 120° C.

GC/MS:

Tandem gas chromatography/low resolution mass spectroscopy usingelectron impact ionization (EI) is performed at 70 eV on an AgilentTechnologies 6890N series gas chromatograph equipped with an AgilentTechnologies 5975 inert XL mass selective detector and an AgilentTechnologies Capillary column (HP1MS, 15 m×0.25 mm, 0.25 micron) withrespect to the following:

Programed method:

Oven Equilibration Time 0.5 min 50° C. for   0 min then 25° C./min to200° C. for   5 min Run Time  11 min

GPC:

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer (Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000 and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)): M_(polyethylene)=0.431(M_(polystyrene)).Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Molecular Weight:

Molecular weights are determined by optical analysis techniquesincluding deconvoluted gel permeation chromatography coupled with a lowangle laser light scattering detector (GPC-LALLS) as described by Rudin,A., “Modern Methods of Polymer Characterization”, John Wiley & Sons, NewYork (1991) pp. 103-112.

Materials

Performance of all examples discussed herein is under an inertatmosphere using dry box techniques unless otherwise stated.

The following materials are obtained from Sigma-Aldrich and purified asneeded prior to use: diisobutylaluminum hydride (DIBAL-H);triisobutylaluminum (TIBA); 5-ethylidene-2-norbornene (ENB);cyclohexene; divinylbenzene; 1,9-decadiene; 1,4-pentadiene;1,3-butadiene; p-xylene; C₆D₆; 4-tert-butylcatechol; toluene; methanol;divinyldichlorosilane; diethylether; phenylmagnesium bromide; hexane;divinyldiphenylsilane; divinyldimethylsilane; THF; vinylmagnesiumbromide; benzene; pentane; D₂O; BHT-benzoic acid; andpentamethylenebis(magnesium bromide).

1,4-bis(chlorodimethylsilyl)benzene and1,5-bis(dimethyl(vinyl)silyl)pentane are obtained from Alfa Aesar.

Isopar™ E is obtained from ExxonMobil Chemical Company.

The activator [HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄] (“Activator A”) is obtained fromBoulder Scientific Co.

The catalyst[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl] (“Catalyst A”) having the structure shown below is preparedaccording to the teachings of WO 03/40195 and WO 04/24740 as well asmethods known in the art.

MMAO-3A is obtained from Akzo Nobel.

Example 1

Preparation of Capped Dual-Headed Organoaluminum Composition Using TIBA,ENB and 1,9-decadiene:

In a nitrogen-filled drybox, TIBA (2.0 mL, 7.9 mmol), 1,9-decadiene (1.1mL, 5.94 mmol), and ENB (1.6 mL, 11.89 mmol) are mixed in 3.5 mL ofp-xylene in a scintillation vial with a stir-bar. This mixture is heatedto and held at 130° C. with stirring for two hours, and a small needleis inserted through the septum cap for venting. After two hours, themixture is clear and viscous, and samples are taken for ¹H NMR and GC/MS(after quenching with water). As seen in FIG. 1, ¹H NMR in C₆D₆ showsthat the intended reaction (see non-limiting Reaction Scheme 1) iscomplete (all vinyl groups are consumed) and the capped dual-headedorganoaluminum composition is formed. As seen in FIG. 2, GC/MS showsmajor peaks at m/z of 122, 142, and 178, which are consistent with theexpected hydrolyzed products of the capped dual-headed organoaluminumcomposition.

Example 2

Preparation of Capped Dual-Headed Organoaluminum Composition Using TIBA,ENB and 1,9-decadiene:

In a nitrogen-filled drybox, ENB (1.6 mL, 11.9 mmol) and TIBA (2.0 mL,7.9 mmol) are mixed in 3.5 mL of p-xylene in a scintillation vial with astir-bar. This mixture is heated to and held at 130° C. with stirringfor two hours, and a small needle is inserted through the septum cap forventing. After two hours, a sample of the mixture (ca 0.1 mL) is takenand mixed with C₆D₆ (0.5 mL) for ¹H NMR (see FIG. 3A), which shows thatall of ENB is consumed. Subsequently, 1,9-decadiene (1.1 mL, 5.94 mmol)is added to the mixture, and heating at 130° C. is continued withstirring for another two hours. Afterwards, the mixture is clear andviscous, and samples are taken for ¹H NMR and GC/MS (after quenchingwith water). As seen in FIG. 3B, ¹H NMR in C₆D₆ shows that the intendedreaction (see non-limiting Reaction Scheme 2) is complete (all vinylgroups are consumed) and the capped dual-headed organoaluminumcomposition is formed. As seen in FIG. 4, GC/MS shows major peaks at m/zof 122, 142, and 178, which are consistent with the expected hydrolyzedproducts of the capped dual-headed organoaluminum composition.

Example 3

Preparation of Capped Dual-Headed Organoaluminum Composition Using TIBA,ENB and Divinylbenzene:

In a nitrogen-filled drybox, TIBA (3.14 mL, 12.46 mmol), ENB (2.80 mL,20.77 mmol) are mixed in 7 mL of p-xylene in a scintillation vial with astir-bar. This mixture is heated to and held at 130° C. while stirringfor 20 minutes, and a small needle is inserted through the septum capfor venting. After 20 minutes, divinylbenzene (1.18 mL, 8.31 mmol, d0.914, 2 equiv; 80%, mixture of m/p isomers, stab. with 1000 ppm4-tert-butylcatechol) is added to the mixture, and heating at 130° C. iscontinued with stirring for three hours. The reaction proceeds asintended (see non-limiting Reaction Scheme 3) to form the dual-headedorganoaluminum composition. The mixture is then allowed to cool to 25°C. Samples are taken for GC/MS and, as seen in FIG. 5, the intendedreaction is confirmed as the expected hydrolyzed products of the cappeddual-headed organoaluminum composition are shown.

Example 4

Preparation of (iBu)₂Al—(CH₂)₅—Al(iBu)₂:

In a nitrogen-filled drybox, neat DIBAL-H (0.8 g, 5.63 mmol) and1,4-pentadiene (0.291 mL, 2.81 mmol) are mixed in 3 mL of p-xylene in ascintillation vial with a stir-bar. This mixture is heated to and heldat 50° C. with stirring for 4.5 hours, then heated to and held at 60° C.for 1 hour. The reaction proceeds as intended (see non-limiting ReactionScheme 4). To confirm the reaction, a small aliquot is dissolved inC₆D₆, quenched with water, and analyzed by ¹H NMR. As seen in FIG. 6A,¹H NMR shows the expected hydrolysis products (isobutene and pentane) ofthe intended reaction. Note: this reaction can also be carried out intoluene or neat.

Preparation of (iBu)HAl—(CH₂)₅—AlH(iBu):

In a nitrogen-filled drybox, ca 5 mL of (iBu)₂Al—(CH₂)₅—Al(iBu)₂ inp-xylene (0.88 M) is heated to and held at 100° C. under vacuum for 14hours. A trap vial is used in this process to capture high-boilingp-xylene, which otherwise would condense in the vacuum tubing. Thereaction proceeds as intended (see non-limiting Reaction Scheme 5). Toconfirm the reaction, an aliquot is diluted with C₆D₆ and a portion ofthis solution is hydrolyzed with water. ¹H NMR spectra are recorded ofthe product (FIG. 6B) and hydrolyzed product (FIG. 6C). Al—H signals areobserved in the ¹H NMR of the non-hydrolyzed sample (2.8-4.0 ppm). The¹H NMR spectrum of the hydrolyzed sample shows the expected hydrolysisproducts, isobutane and pentane, of the intended reaction.

Preparation of Capped Dual-Headed Organoaluminum Composition Using(iBu)HAl—(CH₂)₅—AlH(iBu):

In a nitrogen-filled drybox, neat (iBu)HAl—(CH₂)₅—AlH(iBu) (0.100 g,0.42 mmol) is dissolved in 1.5 mL of toluene, and excess cyclohexene(1.0 mL, 9.87 mmol; d=0.811) is added. The reaction mixture is heated toand held at 90° C. for 14 hours in a sealed vial. The reaction mixtureis reduced to a clear oil under vacuum and heated to and held at 100° C.under vacuum for 14 hours to generate partially capped, C5-linked Al—H.Then the material is dissolved in toluene (0.5 mL), and cyclohexene (0.5mL, 4.99 mmol) is added. The reaction mixture is heated to and held at90° C. with stirring overnight in a sealed vial to complete the intendedreaction (see non-limiting Reaction Scheme 6) to form the cappeddual-headed organoaluminum composition.

Example 5

Preparation of Divinyldiphenylsilane:

A solution of phenylmagnesium bromide (30.18 mmol, 30 mL of 1.0 M indiethylether) is cooled in a glovebox freezer (−30° C.). A solution ofdivinyldichlorosilane (2.1 g, 13.72 mmol) in diethylether (10 mL) isthen added slowly to the phenylmagnesium bromide. This mixture isallowed to stir overnight at room temperature, and the intended reaction(see non-limiting Reaction Scheme 7) proceeds. After the reactionperiod, the volatiles are removed, and the residue is extracted andfiltered using hexane. The removal of the hexane results in an oil withsome cloudiness persisting. The mixture is re-filtered through a smallpad of Celite using hexane as the eluent. Removal of the hexane resultsin the isolation of the desired product as a clear light yellow oil(2.75 g). Column chromatography is performed and results in theisolation of 1.01 g of purified product as a clear oil (1.0121 g,31.2%). ¹H NMR (500 MHz, Benzene-d₆) δ 7.60-7.51 (m, 2H), 7.19-7.09 (m,3H), 6.42 (dd, J=20.2, 14.6 Hz, 1H), 6.08 (dd, J=14.5, 3.7 Hz, 1H), 5.78(dd, J=20.3, 3.7 Hz, 1H). ¹³C NMR (126 MHz, Benzene-d₆) δ 136.08,135.57, 134.19, 133.96, 129.42, 127.84.

Preparation of Capped Dual-Headed Organoaluminum Composition UsingDivinyldiphenylsilane:

DIBAL-H (0.513 g, 3.60 mmol) and ENB (0.722 g, 6.01 mmol) are mixedtogether neat in a glass tube. This mixture is heated to and held at 70°C. for 10 minutes, and then heated to and held at 130° C. for 10minutes; a rubber septa with a needle is inserted to allow venting.After the reaction period, the tube is removed from the heat and cooledto room temperature. Then, divinyldiphenylsilane (0.568 g, 2.40 mmol) isadded to the mixture. The rubber septa is replaced with a Teflon capsealing the reaction vessel, and the mixture is then heated to and heldat 130° C. for an additional 3 hours. After the reaction period, themixture is cooled to room temperature resulting in a clear glassymaterial containing the capped dual-headed organoaluminum composition.

Example 6

Preparation of Capped Dual-Headed Organoaluminum Composition UsingDivinyldimethylsilane:

In a glass tube, DIBAL-H (0.7 g, 4.92 mmol) and ENB (0.986 g, 8.2 mmol)are mixed together neat. This mixture is heated to and held at 70° C.for 10 minutes, and then heated to and held at 130° C. for 10 minutes; arubber septa with a needle is inserted to allow venting. After thereaction period, the tube is removed from the heat and cooled to roomtemperature. Subsequently, divinyldimethylsilane (0.368 g, 3.28 mmol) isadded to the mixture, and the tube is sealed employing a Teflon cap. Themixture is then heated to and held at 70° C. for 5 minutes, and thenheated to and held at 80° C. for 5 minutes. This heating pattern isrepeated with 10° C. increments until the desired temperature of 130° C.is reached. The mixture is then heated at 130° C. for an additional 3hours. The mixture is then cooled to room temperature resulting in aclear viscous oil containing the capped dual-headed organoaluminumcomposition.

Example 7

Preparation of bis(dimethyl(vinyl)silyl)benzene:

1,4-Bis(chlorodimethylsilyl)benzene (4.804 g, 18.24 mmol) in THF (40 mL)is cooled in a glovebox freezer (−30° C.). A solution of vinylmagnesiumbromide (40.14 mmol, 40.14 mL of 1.0 M in THF) is then added slowly.This mixture is allowed to stir to room temperature overnight, and theintended reaction (see non-limiting Reaction Scheme 8) proceeds. Afterthe reaction period, the volatiles are removed and the residue extractedand filtered using benzene. Removal of the benzene from the filtrateresults in the isolation of a free flowing liquid as well as furtherprecipitated salts. This material is filtered through a celite bed usinghexane as the eluent. Removal of the volatiles results in the isolationof the desired product as a clear pale yellow liquid (3.5948 g, 79.9%).¹H NMR (500 MHz, Benzene-d6) δ 7.51 (s, 4H), 6.30-6.19 (m, 1H),5.99-5.91 (m, 1H), 5.69 (dd, J=20.3, 3.8 Hz, 1H), 0.27 (s, 12H). 13C NMR(126 MHz, Benzene-d6) δ 138.86, 137.74, 133.24, 132.59, −3.23.

Preparation of Capped Dual-Headed Organoaluminum Composition Usingbis(dimethyl(vinyl)silyl)benzene:

In a glass tube, DIBAL-H (1.5 g, 10.55 mmol) and ENB (2.113 g, 17.58mmol) are mixed together neat. This mixture is heated to and held at 70°C. for 10 minutes, and then heated to and held at 130° C. for 10minutes; a rubber septa with a needle is inserted to allow venting. Thetube is then cooled to room temperature. Subsequently,1,4-bis(dimethyl(vinyl)silyl)benzene (1.733 g, 7.03 mmol) is added tothe mixture. The rubber septa is replaced with a Teflon cap sealing thereaction vessel. The mixture is then heated to and held at 130° C. foran additional 3 hours. After the reaction period, the mixture is cooledto room temperature resulting in a clear glassy material containing thecapped dual-headed organoaluminum composition.

Example 8

Preparation of 1,5-bis(dimethyl(vinyl)silyl)pentane:

A solution of chlorodimethyl(vinyl)silane (2.654 g, 22 mmol) is dilutedin THF (final volume 20 mL) and cooled in a glovebox freezer (−30° C.).Pentamethylenebis(magnesium bromide) (20 mL, 22 mmol, 1.0 M THF) is thenadded dropwise. The resulting mixture is allowed to stir for 3 hours atroom temperature, and the intended reaction (see non-limiting ReactionScheme 9) proceeds. After the reaction period, the volatiles are removedunder vacuum. The residue comprised of copious gray salts is extractedusing hexane and filtered. Removal of the volatiles results in theisolation of a slightly cloudy pale yellow oil. This oil is passedthrough a short silica gel plug using pentane. Removal of the pentaneresults in the isolation of the desired product as a clear light yellowoil (2.0873 g, 86.8%). ¹H NMR (500 MHz, Benzene-d₆) δ 6.22-6.08 (m, 1H),5.91 (dd, J=14.6, 3.9 Hz, 1H), 5.65 (dd, J=20.4, 3.8 Hz, 1H), 1.35-1.23(m, 3H), 0.57-0.50 (m, 2H), 0.04 (s, 6H). ¹³C NMR (126 MHz, Benzene-d₆)δ 139.21, 131.21, 37.58, 23.75, 23.57, 15.28, −3.63.

Preparation of Capped Dual-Headed Organoaluminum Composition Using1,5-bis(dimethyl(vinyl)silyl)pentane:

In a glass tube, DIBAL-H (3.08 g, 21.66 mmol) and ENB (4.339 g, 36.09mmol) are mixed together neat. This mixture is heated to and held at 70°C. for 10 minutes, and then heated to and held at 130° C. for 10minutes; a rubber septa with a needle is inserted to allow venting.After the reaction period, the tube is cooled to room temperature.Subsequently, 1,5-bis(dimethyl(vinyl)silyl)pentane (1.621 g, 14.44 mmol)is added to the mixture. The rubber septa is replaced with a Teflon capsealing the reaction vessel. The mixture is then heated to and held at130° C. for an additional 3 hours, with the mixture being white andcloudy and able to stir easily despite slight build-up of viscosityduring the early portion of the reaction period. After the reactionperiod, the mixture is cooled to room temperature resulting in aviscous, milky material containing the capped dual-headed organoaluminumcomposition.

Example 9

Preparation of (Cy)₂Al—(CH₂)₄—Al(Cy)₂:

In a glass tube, 1,3-butadiene (24 mmol, 10 mL of 2.4 M in toluene) andDIBAL-H (6.827 g, 48 mmol) are mixed together. This mixture is heated toand held at 70° C. with stirring for a total of 32 hours. The mixture isthen evaporated to dryness under vacuum, and full vacuum is continuedovernight as the residue is heated to and held at 100° C. After thereaction period, the residue is cooled back to room temperature.Subsequently, the residue is heated to and held at 80° C. in cyclohexene(40 mL) in a closed vessel overnight. Following the reaction period, thevolatiles are removed resulting in the isolation of a thick oil. Theresidue is then heated to and held at 100° C. for 3 hours under fullvacuum. After the reaction period, the residue is heated to and held at80° C. in cyclohexene (30 mL) overnight. The volatiles are then removed,and the residue is again heated to and held at 100° C. under full vacuumfor an additional 3 hours. After the reaction period, the residue isheated to and held at 80° C. in cyclohexene (30 mL) overnight. Thisprocess of heating at 80° C. in cyclohexane followed by 100° C. isrepeated a total of 4 times. At this point, the volatiles are removedunder vacuum resulting in the isolation of a sticky residue containingthe capped dual-headed organoaluminum composition.

Example 10

Preparation of (iBu)₂Al—(CH₂)₂—C₅H₈—(CH₂)₂—Al(iBu)₂:

In a nitrogen-filled drybox, neat DIBAL-H (1.00 mL, 5.61 mmol, d=0.798)and 1,3-divinylcyclopentane solution (30.9 wt % in toluene, 1.11 g, 2.81mmol) are mixed in a capped scintillation vial with a stir-bar. Thismixture is heated to and held at 90° C. with stirring for 18 hours. Thereaction proceeds as intended (see non-limiting Reaction Scheme 10) toform the dual-headed organoaluminum composition. To confirm thereaction, an aliquot of the mixture is diluted with C₆D₆, hydrolyzedwith 10 wt % NaOD in D₂O, and analyzed by ¹H NMR and ¹³C NMR. As seen inFIGS. 5A and 5B, ¹H NMR and ¹³C NMR show the expected hydrolysis product1,3-bis(ethyl-2-d)cyclopentane of the dual-headed organoaluminumcomposition. The hydrolyzed sample is also analyzed by GC/MS, whichshows a clean peak with m/z of 128 that is consistent with the expectedhydrolyzed product of the dual-headed organoaluminum composition.

Preparation of (Cy)₂Al—(CH₂)₂—C₅H₈—(CH₂)₂—Al(C_(y))₂.

The title compound can be made following synthetic procedures shown inexample 4 and non-limiting reaction scheme 11.

Polyethylene Polymerization

In a nitrogen-filled drybox, a vial equipped with a stir-bar is chargedwith Isopar™ E (10 mL) and Activator A (0.04 mL, 0.0024 mmol, 0.064 M).The vial is sealed with a septum cap and placed in a heating block setto 100° C. An ethylene line (from a small cylinder) is connected and thevial headspace is slowly purged via a needle. The capped dual-headedorganoaluminum composition prepared in Example 3 (0.37 mL, 0.30 mmol,0.815 M based on divinylbenzene) and Procatalyst A (0.10 mL, 0.002 mmol,0.02 M) are injected, and the purge needle is removed to maintain atotal pressure at 12 psig. The reaction mixture is stirred for 30 min,then taken out of the drybox and quenched with MeOH (100 mL). Theprecipitated white polymer is stirred in methanol for 3 hours, followedby filtration and drying of the polymer under vacuum overnight (0.265g). ¹³C NMR shows the aromatic signals from the incorporateddivinylbenzene and the saturated polymer chain ends (FIG. 7). GPCresults: M_(n)=1,512; M_(w)=3,880; PDI=2.57. The GPC chromatogram isshown in FIG. 8. This exemplary polymerization of polyethylene isexemplified below in non-limiting Reaction Scheme 12.

Copolymer Polymerization in HOPR Reactor

General HOPR Information:

All chemicals used are either purchased as anhydrous reagents orthoroughly degassed before introduction into an MBraun drybox. Allmanipulations are performed while working in a nitrogen-filled drybox.Toluene, Isopar™ E, 1-octene, and ethylene gas are purified and dried bypassing through a bed of Q-5 catalyst. All of the reactor chemistry isdone using the HOPR equipped with a Xantus robotic workstation model 4400/100. Both the liquid handler and reactor are installed in an MBraundrybox enabling liquid handling manipulations under an inert nitrogenatmosphere. The reagent solutions are made in the drybox prior to theexperiment. The MMAO-3A are used either as the original stock 1.9 Msolution or diluted with toluene. The 18×54 mm round bottom reactortubes in the 24 well plate (4×6) are tared and weighed on the ABD weighstation. All reactor tubes are dried down using a Thermo Savant modelSC250EXP for 10 hours at 80° C. Heating of the reactor is done using aMokon HTF system model H54124NR.

Representative HOPR Synthetic and Screening Procedure:

A 24 well plate (4×6) with 18×54 mm round bottom reactor tubes is placedon the deck of the Tecan. To each reactor tube is added MMAO-3A (20nmoles), Activator A (1.2 nmoles), 1-octene (100 μL), a cappeddual-headed organoaluminum composition from a particular example (10 or25 mmoles), and Isopar™ E (such that the final volume will be 5.0 mL).These reactor tubes are then placed into the HOPR which is at 20° C.with the lid secured. Then, magnetic stirring starts. The reactor isthen pre-pressurized with 75 psi of ethylene gas. Next, the reactor isheated to the temperature of 100° C. The reactor is then fullypressurized to 150 psi. Catalyst A (1 nmole) is then added to eachreactor tube to initiate the polymerization. After 5 minutes, aBHT/Benzoic acid quench is added and then the reactor is cooled andslowly vented. The lid is removed and the tubes are placed back into the4×6 rack to be dried down in the Savant and then weighed to obtain themass of ethylene/octene copolymer produced followed by GPC analysis ofthe polymers. The polymerization data is presented below in Table 1.

TABLE 1 Composition Composition Loading Isolated (Example #)(micromoles) Polymer (g) M_(w) (g/mol) M_(n) (g/mol) PDI None 0 0.0872,139,010 472,460 4.53 3 25 0.277 85,080 23,910 3.56 3 25 0.153 115,08019,610 5.87 3 25 0.317 76,800 21,140 3.63 5 10 0.268 82,880 31,030 2.675 25 0.284 50,660 20,260 2.50 5 25 0.316 49,630 17,190 2.89 6 10 0.30040,530 17,580 2.30 6 10 0.293 39,250 16,410 2.39 6 25 0.263 24,240 9,6102.52 6 25 0.255 21,750 8,730 2.49 7 10 0.118 402,110 68,090 5.91 7 100.123 307,640 24,760 12.42 7 25 0.142 257,080 23,190 11.09 7 25 0.143256,340 16,880 15.18 8 10 0.214 82,970 30,910 2.68 8 10 0.197 85,97029,620 2.90

What is claimed is:
 1. A composition of formula (I):

wherein: n is a number from 1 to 100; Y is a linking group composed of alinear, branched, or cyclic C₄ to C₁₀₀ hydrocarbylene group thatoptionally includes at least one heteroatom and that is aliphatic oraromatic, wherein Y comprises two points of attachment to Al atoms andat least one of the two points of attachment is —CH₂—; each R group isindependently a substituted or unsubstituted aryl group or a substitutedor unsubstituted cyclic alkyl group containing, optionally, at least oneheteroatom; and two R groups attached to the same Al can be optionallycovalently linked together.
 2. The composition of claim 1, wherein eachR group is independently selected from the group consisting of thefollowing structures CG1 to CG4:

wherein: each R₁ is independently hydrogen or a C₁ to C₂ alkyl group;each X₂, X₃, X₄, and X₅ is independently hydrogen, a substituted orunsubstituted C₁ to C₂₀ alkyl, alkylene or alkylidene group, or asubstituted or unsubstituted C₆ to C₂₀ aryl group; each X₂, X₃, X₄, andX₅ optionally includes at least one heteroatom; and in each ofstructures CG1 to CG3, two of the groups selected from X₂, X₃, X₄, andX₅ may optionally join to form cyclic structures.
 3. The composition ofclaim 1 or 2, wherein each R group is independently selected from thegroup consisting of the following structures CG5 to CG13:

wherein each R₁ is independently hydrogen or a C₁ to C₂₀ alkyl group. 4.The composition of any of the preceding claims, wherein each R group isCG5 or CG12.
 5. The composition of any of the preceding claims, whereinY has the formula (II):—CH₂CH₂(CHR₂)_(m)CH₂CH₂—  (II), wherein: R₂ is hydrogen or a C₁ to C₂₀alkyl or aryl group; and m is a number from 0 to
 20. 6. The compositionof any of claims 1-4, wherein Y has the formula (III):—CH₂CH₂—Z—CH₂CH₂—  (III), wherein: Z is a C₄ to C₁₀₀ hydrocarbylenegroup comprising at least one aliphatic or aromatic ring and,optionally, includes at least one heteroatom.
 7. The composition of anyof the preceding claims, wherein Y is a derivative of a linking agentselected from the group consisting of 1,9-decadiene, 1,4-pentadiene,divinylbenzene, divinyldiphenylsilane, divinyldimethylsilane,1,4-bis(dimethyl(vinyl)silyl)benzene,1,5-bis(dimethyl(vinyl)silyl)pentane, and 1,3-divinylcyclopentane. 8.The composition of any of the preceding claims, wherein n is a numberfrom 1 to
 10. 9. The composition of claim 8, wherein n is a number from1 to
 3. 10. A process for preparing a composition, the processcomprising: (a) combining an aluminum compound, a linking agent, acapping agent, and an optional solvent at a temperature of from 50° C.to 200° C. for a time from 30 minutes to 200 hours, and (b) obtainingthe composition, wherein: the aluminum compound has the formula Al(J)₃,wherein each J group is independently hydrogen, a substituted orunsubstituted alkyl group, or a substituted or unsubstituted aryl orheteroaryl group, wherein at least one J group is a hydrogen or anacyclic alkyl group and, optionally, two J groups can be covalentlylinked together; the linking agent is a C₄ to C₁₀₀ hydrocarboncomprising either at least two vinyl groups or a vinyl group and acyclic olefin group and, optionally, includes at least one heteroatom;and the capping agent is a substituted or unsubstituted cyclic olefin.11. The process of claim 10, wherein the capping agent is selected fromthe group consisting of the following structures CA1 to CA4:

wherein: each X₂, X₃, X₄, and X₅ is independently hydrogen, asubstituted or unsubstituted C₁ to C₂₀ alkyl, alkylene or alkylidenegroup, or a substituted or unsubstituted C₆ to C₂₀ aryl group; each X₂,X₃, X₄, and X₅ optionally includes at least one heteroatom; and in eachof structure CA1 to CA3, two of the groups selected from X₂, X₃, X₄, andX₅ may optionally join to form cyclic structures.
 12. The process ofclaim 11, wherein the capping agent is selected from the groupconsisting of the following structures CG5 to CG10:


13. The process of claim 12, wherein the capping agent is CG5 or CG9.14. The process of any of claims 10-13, wherein the aluminum compound istriisobutylaluminum or diisobutylaluminum hydride.
 15. The process ofany of claims 10-14, wherein the linking agent is selected from thegroup consisting of 1,9-decadiene, 1,4-pentadiene, divinylbenzene,divinyldiphenylsilane, divinyldimethylsilane,1,4-bis(dimethyl(vinyl)silyl)benzene,1,5-bis(dimethyl(vinyl)silyl)pentane, and 1,3-divinylcyclopentane
 16. Acomposition comprising the reaction product of: an aluminum compound, alinking agent, a capping agent, and an optional solvent, wherein: thealuminum compound has the formula Al(J)₃, wherein each J group isindependently hydrogen, a substituted or unsubstituted alkyl group, or asubstituted or unsubstituted aryl or heteroaryl group, wherein at leastone J group is a hydrogen or an acyclic alkyl group, and optionally, twoJ groups can be covalently linked together; the linking agent is a C₄ toC₁₀₀ hydrocarbon comprising either at least two vinyl groups or a vinylgroup and a cyclic olefin group and, optionally, includes at least oneheteroatom; and the capping agent is a substituted or unsubstitutedcyclic olefin.
 17. A polymerization process for preparing a polymercomposition, the process comprising: (a) contacting at least one olefinmonomer with a catalyst composition, wherein the catalyst compositioncomprises the reaction product of at least one catalyst precursor, atleast one co-catalyst, and the composition of claim 1, and (b) obtainingthe polymer composition.
 18. A polymer composition prepared by theprocess of claim 17, wherein the polymer composition comprises twoaluminum termini.
 19. A process for preparing a polymer or a polymermixture by converting polymer-Al bonds of the polymer composition ofclaim 18 using either a chemical reagent or high temperature.